Method for the manufacture of basic substituted carboxylic acid amides



Patented Jan. 9

' UNITED STATES rm'rnon ron MANUFACTURE OF THE BASIC SUBSTITUTED CARBOXYLIC ACID AMIDES Erik Schirm, Dessau, Anhalt, Germany, assignmto Deutsche Hydrierwerke Aktiengescllschaft, Berlin-Charlottenburg, Germany, a corporation of Germany No Drawing. Application October 14,1936, Serial No. 105,518. In Germany October 16', 1935 16 Claims.

It has been found that valuable basic carboxylic acid amides can be obtained by the reaction of carboxylic acids which contain in the molecule basic nitrogen atoms unbound with hydrogen atoms, or their inner molecular salts or their salts formed with acids or bases, upon organic compounds containing primary or secondary amino-groups in the presence of any waterbinding media. The conversion is advantal0 geously accomplished in the presence of an inert diluting agent.

The nitrogen atoms of the aforementioned carboxylic acids may be in the form of tertiary amines or of quaternary ammonium compounds.

In both cases the nitrogen atom may also be a component-part of a heterocyclic ring-system. As examples of -the former may be mentioned: dimethyl-amino-acetic acid, N-piperidino-acetic acid, the three dimethyl-amino-benzoic acids,

20 the three pyridine-mono-carboxylic acids, the

various pyridine-di-carboxylic acids, quinolinecarboxylic acids and others. In the second place the group comprises such compounds as: betaine and its homologues, trimethyl-mor -p-benzbetaine, as well as the addition products of alkylor of aralkyl-halides or of dialkyl sulfates or aryl sulfonic acid-alkyl esters on dimethyl-amia no-acetic acid and on the other aforesaid car-' boxylic acids containing a tertiary nitrogen atom. The amino-compounds suitable for the present method may be of quite varied constitution. All primary and secondary amines of the allphatic, aromatic, mixed aliphatic-aromatic and 'heterocyclic series are applicable. The amines may also contain any substitue'nts whatever, provided they do not react or interfere with the conversion in question. In applying amino-compounds, whose mineral acid salts do not hydrolyze or hydrolyze only slightly in water, i. e., 40 such as salts of alkyl-amines or aniline and its homologues, it has proved desirable to accomplish the condensation in the presence of tertiary amines, such as tri-ethyl-amine, dimethyl-aniline or pyridine. The aforesaid tertiary amines may also serve as diluting agents. With particularly low-basic amines, e. g., with diphenylamine, p-nitraniline or with the amino-anthraquinones, one can do without such addition.

As dehydrating agents the phosphor-halides and phosphor-oxyhalides as well as thionylchloride are primarily to be considered. Though the processor condensing carboxylic acids with amines'by means of dehydrating agents is already known, it is, however, new and quite surprising, that carboxylic acids which contain a basic and nitrogen-bearing residue are likewise operable in a condensation process, as indeed it was rather to be expected that by the basic residue the reactivity of the carboxylic acids would be considerably reduced. This applies particularly to 5 betaine and other compounds belonging to the same class and being of a betaine like structure, which compounds represent "inner salts. The latter as' well as their mineral acid-addition products such as betaine-hydrochloride, are 10 practically insoluble in the usual inert diluting agents such as hydrocarbons and halogen-hydrocarbons, nitrobenzene and the like. It is for this reason too that the course of the new condensation-reaction could not be expected. 1

The technical progress of the present method is evident when in one single operation, starting from the carboxylic acids with either. a tertiary or quaternary nitrogen atom, which in many cases are readily obtainable, one directly attains 20 the substituted basic carboxylic acid-amides which are useful in many commercial operations, and which according to the hitherto-known methods could only be obtained by a sequence of various operations. 25

It is known that betaine is found in considerable amounts in the spent wash of molasses .and in the manufacture of beet. Hence sugar the present method is also of a great economic importance due to the fact that in this way the betaine can, for the first time, be utilized in the form of derivatives of high value.

Example 1 185 parts by weight of n-dodecyl-amine are 35 dissolved in 300 parts of pyridine. This solution is added to 3000 parts of toluol, whereupon 117 parts of finely pulverized dry betaine are suspended therein, 125 parts of Dhosphor-trichloride are then slowly added and the mixture is 40 gradually heated to C. under permanent and vigorous stirring. At this temperature one continues stirring for 3 to 4 hours, then the mixture is cooled down to room-temperature and the crystalline precipitate is sucked off. The latter 5 consists of the N-dodecyl-acetamide-w-tri methyl-ammonium chloride, which is readily soluble, in water, gives copious lather and cannot be salted out by common salt from this solution, while with potassium-iodide it can be separated 5 in the form of iodide (melting point 176-1'77 C.) and isreadily easily soluble in hot water and with some difliculty in cold water.

The above described compound may advantageously be used for all purposes for which one 55 cooled down, whereby the condensation-product is almost completely separated oi! in the form 01' the bromide. Its constitution formula is most probably as follows:

atom on the nitrogen atom in the presence of water-binding agents.

2. Method for the manufacture of basic substituted carboxylic acid amides comprising the ther before or after the dyeing with the acid sub-- stantive dyestufi.

Example 7 165 parts by weight of N-piperidino-acetic acid sodium in a finely pulverized form are introduced into 1500 parts by volume of monochlorobenzene; then one adds 93 parts by weight of aniline, 250 of pyridine, and then finally stirs in 125 parts of phosphor-trichloride gradually. Now one heats the mixture to 110 C. and at this temperature continues stirring for 3 hours, whereupon the mixture is cooled. It is then diluted with 1000 parts of water and rendered litmus-neutral, whereupon any volatile matters are blown off by water-vapour. When the product has grown cold it is filtered on and the residue is dissolved in 2500 parts of boiling water after an addition of just enough hydrochloric acid to attain a slight Congo-acid reaction of the liquid. Now the mixture is filtered from the insoluble resinous residue and the filtrate is cooled in ice after an addition of 700 parts of common salt, whereby the reaction-product (which will be of the formula of a w-piperidinoacetanilide) is separated as chlorohydrate in the form of small colourless leaves. The precipitate is filtered and dried, its melting point being 180 to 181 C.

Example 8 123 parts by weight of picolinic acid and 138 parts of p-nitraniline are finely pulverized and suspended in 1500 parts by volume of nitrobenzene, whereupon 1'75 weight-parts of thionylchloride are stirred in. Now the mixture isv heated for about 4 hours, while being stirred up to 105 to 110 C. until the development of gas, which begins at about C.. is finished. When the reaction mass has grown cold the light powdery residue is filtered off. the sticky nitrobenzene is washed out with cold alcohol and then it is dried at 100 C. The yield of raw picoloyl-p-nitraniline (picolinic acid-p-nitranilide) is 92% of the theoretical amount. The product can be purified by re-crystallizing from a large amount 'of boiling pyridine. By heating it carbonizes at approximately 300 C. without melting.

By the reduction of the nitro-group to the amino-group one comes to the picoloyl-p-phenylene-diamine (picolinic acid-p-amino-anilide) which forms a valuable diazo component for the preparation of substantive azo-dyestufis.

I claim:

1. Method for the manufacture of basic substituted carboxylic acid amides comprising the condensation of carboxylic acids containing basic nitrogen atoms unbound with hydrogen atoms with amines containing at least one hydrogen condensation of carboxylic acids containing basic groups selected irom the group consisting of tertiary amino groups and quaternary ammonium groups and amines containing at least one hydrogen atom on the nitrogen atom in the presence of water-binding agents.

3. Method for the manufacture of basic substituted carboxylic acid amides comprising the condensation of carboxylic acids containing basic nitrogen atoms unbound with hydrogen atoms with organic amino compounds of the group consisting of primary and secondary amines of the aliphatic, aromatic, aliphatic-aromatic and beterocyclic series in the presence of water-binding agents.

4. Method for the manufacture of basic substituted carboxylic acid amides comprising the condensationoi' carboxylic acids containing basic nitrogen atoms unbound with hydrogen atoms with substituted organic amino compounds of the group consisting of primary and secondary amines of the aliphatic, aromatic, aliphatic-aromatic and heterocyclic series in the presence of water-binding agents.

5. Method for the manufacture 01' basic substituted carboxylic acid amides comprising the condensation of carboxylic acids containing tertiary amino groups of .the group consisting of dialkyl-amino-acetic acids, N-piperidino-acetic acid, the three dimethyl-amino-benzoic acids, the three pyridine-'mono-carbonic acids, the pyridine-dicarboxylic acids, the. quinoline-carboiwlic acids with amines containing at least one hydrogen atom on the nitrogen atom in the pres-' mg of betaine and its homologues. trimethyl-m- I benzbetaine, trimethyl-p-benzbetaine, addition products of alkyl-halides, aralkyl-halides, dialkyl-suliates, aryl-sulionic acid-alkyl-esters on di-alkyl-amino-acetic acids with amines containing at least one hydrogen atom on the nitrogen atom in the presence of water-binding agents.

'7. Method for the manufacture of basic substituted carboxylic acid amides comprising the condensation oi carboxylic acids containing basic nitrogen atoms unbound with hydrogen atoms and amines containing at least one hydrogen atom on the nitrogen atom in the presence of water-binding agents and in the presence of tertiary amines.

8. Method for the manufacture oi basic substituted carboxylic acid amides comprising the condensation of salts of the carboxylic acids containing basic nitrogen atoms unbound with hydrogen atoms of the group consisting of salts formed with acids, salts formed with bases and inner molecular salts with amines containing at least one hydrogen atomon the nitrogen atom in the presence of water-binding agents.

9. Condensation products of 'carboxylic acids containing basic nitrogen atoms unbound with hydrogen atoms, and amines containing at least one hydrogen atomv and a hydrocarbon radical of at least 6 carbon atoms on the, nitrogen atom.

10. Condensation products of carboxylic acids containing basic groups of the'class consisting of tertiary amino groups and quaternary ammonium groups, and amines containing at-least one hydrogen atom and a hydrocarbon radical of at least 6 carbon atoms on the nitrogen atom.

11. Condensation products or carboxylic acids containing basic nitrogen atoms unbound with hydrogen atoms, and organic amino compounds of the group consisting of primary and secondary amines of the aliphatic, aromatic, aliphaticaromatic and heterocyclic series having a radical attached to the amine nitrogen atom containing at least 6 carborr atoms.

12. Condensation products of carboxylic acids containing basic nitrogenatoms unbound with hydrogen atoms, and substituted organic amino compounds of thegroup consisting of primary and secondary amines of the aliphatic, aromatic, aliphatic-aromatic and heterocyclic series having a radical attached to the amine nitrogen atom containing at least 6 carbon atoms.

13. A new compound, N-dodecyl-acetamide-wtrimethyl-ammonium chloride.

14. A new compound, acetyl-p-nitraniline-wtrime'thyl-ammonium chloride.

15. Acetyl-u-amino-anthraqu1inone-w-trimethyl-ammonium chloride.

16. The process of producing basic substituted carboxylic acid amides comprising the step of condensing carboxylic acids containing basic nitrogen atoms unbound with hydrogen atoms with amines containing at least one hydrogen atom and a hydrocarbonradical of at least 6 carbon atoms, in the presence of a water-binding agent.

ERIK SCHIRM.

. CERTIFICATE OF coRR cTIoN. Patent No. 2,186,769. v January 9, 191m.

ERIK SCHIRM.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 1, sec- 0nd column; line 28 strike out the word "sugar" and insert the same after "beet" and before the period in same line; and that the said Letters Patent should be read with this correction therein that the same may conform I to the record of the casein the Patent Office.

Signed and sealed this 12th day of March, A. 19L;o.

- I Y Henry'Van arsdale, (Seal) I Acting Commissioner of Patents. 

